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1. Introduction
The residual dyes from different sources (e.g., textile industries, paper and pulp industries,
dye and dye intermediates industries, pharmaceutical industries, tannery, and Kraft
bleaching industries, etc.) are considered a wide variety of organic pollutants introduced
into the natural water resources or wastewater treatment systems.
One of the main sources with severe pollution problems worldwide is the textile industry
and its dye-containing wastewaters (i.e. 10,000 different textile dyes with an estimated
annual production of 7.105 metric tonnes are commercially available worldwide; 30% of
these dyes are used in excess of 1,000 tonnes per annum, and 90% of the textile products are
used at the level of 100 tonnes per annum or less) (Baban et al., 2010; Robinson et al., 2001;
Soloman et al., 2009). 10-25% of textile dyes are lost during the dyeing process, and 2-20%
are directly discharged as aqueous effluents in different environmental components.
In particular, the discharge of dye-containing effluents into the water environment is
undesirable, not only because of their colour, but also because many of dyes released and
their breakdown products are toxic, carcinogenic or mutagenic to life forms mainly because
of carcinogens, such as benzidine, naphthalene and other aromatic compounds (Suteu et al.,
2009; Zaharia et al., 2009). Without adequate treatment these dyes can remain in the
environment for a long period of time. For instance, the half-life of hydrolysed Reactive Blue
19 is about 46 years at pH 7 and 25°C (Hao et al., 2000).
In addition to the aforementioned problems, the textile industry consumes large amounts of
potable and industrial water (Tables 1, 2 and Fig. 1) as processing water (90-94%) and a
relatively low percentage as cooling water (6-10%) (in comparison with the chemical
industry where only 20% is used as process water and the rest for cooling). The recycling of
treated wastewater has been recommended due to the high levels of contamination in
dyeing and finishing processes (i.e. dyes and their breakdown products, pigments, dye
intermediates, auxiliary chemicals and heavy metals, etc.) (Tables 3, 4 and 5) (adapted from
Bertea A. and Bertea A.P., 2008; Bisschops and Spanjers, 2003; Correia et al., 1994; Orhon et
al., 2001).
Organic Pollutants Ten Years After
56 the Stockholm Convention – Environmental and Analytical Update
Fig. 1. Specific water consumption in different operations of textile finishing (EPA, 1997)
The most common textile processing technology consists of desizing, scouring, bleaching,
mercerizing and dyeing processes (EPA, 1997):
• Sizing is the first preparation step, in which sizing agents such as starch, polyvinyl
alcohol (PVA) and carboxymethyl cellulose are added to provide strength to the fibres
and minimize breakage.
• Desizing is used to remove sizing materials prior to weaving.
• Scouring removes impurities from the fibres by using alkali solution (commonly sodium
hydroxide) to breakdown natural oils, fats, waxes and surfactants, as well as to emulsify
and suspend impurities in the scouring bath.
• Bleaching is the step used to remove unwanted colour from the fibers by using
chemicals such as sodium hypochlorite and hydrogen peroxide.
• Mercerising is a continuous chemical process used to increase dye-ability, lustre and
fibre appearance. In this step a concentrated alkaline solution is applied and an acid
solution washes the fibres before the dyeing step.
• Dyeing is the process of adding colour to the fibres, which normally requires large
volumes of water not only in the dye bath, but also during the rinsing step. Depending
on the dyeing process, many chemicals like metals, salts, surfactants, organic processing
aids, sulphide and formaldehyde, may be added to improve dye adsorption onto the
fibres.
In general, the textile industry uses a large quantity of chemicals such as:
• Detergents and caustic, which are used to remove dirt, grit, oils, and waxes. Bleaching is
used to improve whiteness and brightness.
• Sizing agents, which are added to improve weaving.
• Oils, which are added to improve spinning and knitting.
• Latex and glues, which are used as binders.
• Dyes, fixing agents, and many in-organics, which are used to provide the brilliant array of
colours the market demands.
• A wide variety of special chemicals, which are used such as softeners, stain release agents,
and wetting agents.
Many of these chemicals become part of the final product whereas the rest are removed
from the fabric, and are purged in the textile effluent.
Type of finished textile product Dyes, g/kg Auxiliaries, g/kg Basic chemical
textile textile product compounds, g/kg
product textile product
Polyester fibres 18 129 126
Fabrics from synthetic fibres 52 113 280
Fabrics from cotton 18 100 570
Dyed fabrics from cellulose fibres 11 183 200
Printed fabrics from cellulose fibres 88 180 807
Table 3. Principal pollutants of textile wastewaters (EWA, 2005)
The annual estimated load with pollutants of a textile wastewater is of: 200,000-250,000 t
salts; 50,000-100,000 t impurities of natural fibres (including biocids) and associated
materials (lignin, sericine, etc.); 80,000-100,000 t blinding agents (especially starch and its
derivatives, but also polyacrylates, polyvinyl alcohol, carboxymethyl cellulose); 25,000-
Organic Pollutants Ten Years After
58 the Stockholm Convention – Environmental and Analytical Update
30,000 t preparation agents (in principal, mineral oils); 20,000-25,000 t tensides (dispersing
agents, emulsifiers, detergents and wetting agents); 15,000-20,000 tonnes carboxylic acids
(especially acetic acid); 10,000-15,000 t binders; 5,000-10,000 t urea; 5,000-10,000 t ligands,
and < 5,000 t auxiliaries (EWA, 2005). The environmental authorities have begun to target
the textile industry to clean up the wastewater that is discharged. The principal quality
indicators that regulators are looking for polluting effect or toxicity are the high salt content,
high Total Solids (TS), high Total Dissolved Solids (TDS), high Total Suspended Solids
(TSS), Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD), heavy
metals, colour of the textile effluent (ADMI color value - American Dye Manufacturer
Institute color value), and other potential hazardous or dangerous organic compounds
included into each textile processing technological steps (Tables 4 and 5).
85% or concentration values of the specific quality indicators under the imposed or standard
limits) (Zaharia, 2008).
The decolorization treatments applied for different textile effluents include current and also
advanced non-biological (i.e. specific mechano-physical, chemical, electrochemical process-
es, etc.) and also biological processes (Suteu et al., 2009; Zaharia, 2006; Zaharia et al, 2011).
Table 6. Romanian national wastewater and water quality standard adapted to European
and international standards (adapted from Zaharia, 2008)
Studies on the behavior of textile organic dyes in water and wastewater treatment
processes refer predominantly to laboratory tests or investigations of semi-technical
plants, sometimes under conditions related to waterworks practice. In addition, textile
operators, water supply companies, local environmental authorities have collected a lot of
data on the behavior of textile dyes during textile wastewater treatment, but have seldom
published their results.
However, information on the behavior of textile organic dyes is needed, because the limited
number of reports available that are based on realistic operating conditions or which
reproduce practical conditions that are already several years old.
reactive dyes, etc. The most problematic dyes are those which are made from known
carcinogens such as benzidine and other aromatic compounds (i.e. anthroquinone-based
dyes are resistant to degradation due to their fused aromatic ring structure). Some disperse
dyes have good ability to bioaccumulation, and the azo and nitro compounds are reduced in
sediments, other dye-accumulating substrates to toxic amines (e.g. R1-N=N-R2 + 4H+ + 4e- →
R1-NH2 + R2-NH2).
The organic dyes used in the textile dyeing process must have a high chemical and
photolytic stability, and the conventional textile effluent treatment in aerobic conditions
does not degrade these textile dyes, and are presented in high quantities into the natural
water resources in absence of some tertiary treatments.
Reactive Orange 16
OH
O C.I. 18097
N
a
O
S
O
C
H
-
C
H
-
S
O
3
Methylene Blue
N (Basic Blue 9)
C.I. 52015
+
S
Cationic, phenothiazine dye;
N(CH3)2
(CH3)2N Cl- MW =319.85 g/mol;
λmax= 660 nm
The major textile dyes can be included in the two high classes: azo or anthraquinone (65-
75% from total textile dyes). The azo dyes are characterised by reactive groups that form
covalent bonds with HO-, HN-, or HS- groups in fibres (cotton, wool, silk, nylon). Azo dyes
are mostly used for yellow, orange and red colours. Anthraquinone dyes constitute the
second most important class of textile dyes, after azo dyes, and have a wide range of colours
in almost the whole visible spectrum, but they are most commonly used for violet, blue and
green colours (Fontenot et al., 2003). Considering the nature of textile fibres that are dyeing,
the textile dyes can be classified as into Table 9.
Methylenedianiline - 398 (b.p.), kH= 5.67E-06, Csatw= 1000, pKa= n.s., log Kow= 1.59; for 4-
Aminodiphenylamine - 354 (b.p.), kH= 3.76E-01, Csatw= 1450, pKa= 5.2, log Kow= 1.82;
where, kH - the Henry’s constant at 1013 hPa and 25°C (Pa.m3/mol), Csatw - the water
solubility (mg/L) at 25°C, pKa – dissociation constant of the protonated azo dye at 25°C,
Kow – n-octanol/water partition coefficient, n.s. – not specified)
• toxicological studies (i.e. acute toxicity-oral, inhalation, dermal, skin or eyes irritation,
skin sensitisation, repeated dose toxicity-28 days, mutagenicity, toxicity to
reproduction, toxicokinetic behaviour),
• ecotoxicological studies (i.e. acute toxicity to fish, daphnia, growth inhibition on algae,
bacteriological inhibition, degradation: ready biodegradability, abiotic degradation-
hydrolysis as a function of pH, BOD, COD, BOD/COD ratio).
These characteristics and indentification data are given obligatory by the dye producers or
distributors of textile products on the free market of homologated colorants, and also exist
in the library data of some operating programs of advanced analysis apparatus.
The textile azo dyes are characterized by relatively high polarity (log Kow up to 3) and high
recalcitrance. Recalcitrance is difficult to evaluate because of the dependence of degradation
on highly variable boundary conditions (e.g., redox milieu or pH). For example, aniline (the
first synthetic discovered dye) is known to be easily degradable, but under specific anoxic
conditions it has been proven to be easily stable (Börnick and Schmidt, 2006). Furthermore,
the azo dyes are relevant in terms of eco- and human toxicity, industrially produced in high
quantities, and known to occur in hydrosphere.
The azo dyes can accept protons because of the free electron pair of the nitrogen, and the
free electron pair of nitrogen interacts with the delocalized π-orbital system.
Acceptor substituients at the aromatic ring such as –Cl or –NO2 cause an additional decrease
in the basic character of aminic groups. Donor groups such as –CH3 or –OR (in metha and
para position) lead to an increase in the basicity of aromatic aminic groups. However, donor
substituients in the ortho position can sterically impede the protonation and consequently
decrease the basicity of aminic groups. The azo dyes are characterized by amphoteric
properties when molecules contain additional acidic groups such as hydroxyl, carboxyl or
sulfoxyl substituents.
Depending on pH value, the azo dyes can be anionic (deprotonation at the acidic group),
cationic (protonated at the amino group) or non-ionic. Accordingly, knowledge of the
acidity constants is indispensable for the characterization of the behavior of azo dyes.
Environmental partitioning is influenced by substituents as well as the number of carbon
atoms and aromatic structure of the carbon skeleton. The presence of an amino group causes
a higher boiling point, a higher water solubility, a lower Henry’s law constant, and a higher
mobility in comparison with hydrocarbons (the amino group can also reduce the mobility
by specific interactions with solids via covalent bonding to carbonyl moieties or cation
exchange) (Börnick and Schmidt, 2006). The volatility of azo dyes in aqueous solution is in
most cases very low. Some colour characteristics from different studies, tests and literature
data are presented in Table 10, especially for reactive dyes.
The chromophore distribution in reactive dyes indicated that the great majority of
unmetallised azo dyes are yellow, orange and red. Contrarily, the blue, green, black and
brown contain a much more proportion of metal-complex azo, anthraquinone,
triphenyldioxazine or copper phthalocyanine chromophores (Table 10).
Textile Organic Dyes – Characteristics, Polluting Effects
and Separation/Elimination Procedures from Industrial Effluents – A Critical Overview 65
Chemical class Yellow Orange Red Violet Blue Green Brown Black Proportion
of all
reactive
dyes
Unmetallised azo 97 90 90 63 20 16 57 42 66
Metal complex azo 2 10 9 32 17 5 43 55 15
Anthraquinone - - - 5 34 37 - 3 10
Phthalocyanine - - - - 27 42 - - 8
Miscellanous 1 - 1 - 2 - - - 1
Table 10. Distribution of chemical classes in reactive dye range (adapted from Cooper, 1995)
In general, colour in wastewater is classified in terms of true/real colour (i.e. colour of
turbidity-free water sample), or apparent colour (i.e. colour of non-treated water sample).
The most common methods to measure the colour of dye solution or dispersion, and/or
wastewater are visual comparison and spectrophotometry, although there is still a lack of an
universal method to classify coloured wastewater discharges. By visual comparison, colour is
quantified by comparing the colour of sample with either known concentrations of coloured
standards (normally a platinum-cobalt solution), or properly calibrated colour disks, and is
less applicable for highly coloured industrial wastewaters. In the spectrophotometric method,
colour-measuring protocols differ between the methodologies, of which the most commonly
used are Tristimulus Filter Method, American Dye Manufacturer Institute (ADMI)
Tristimulus Filter Method, and Spectra record (Table 11).
Spectrophotometric Description
method
Tristimulus Three tristimulus light filters combined with a specific light source
(i.e. tungsten lamp) and a photoelectric cell inside a filter
photometer. The output transmittance is converted to trichromatic
coefficient and colour characteristic value.
ADMI Tristimulus The ADMI colour value provides a true watercolour measure,
which can be differentiated in 3 (WL) ADMI (i.e. the transmittance
is recorded at 590, 540 and 438 nm) or 31 (WL) ADMI (i.e. the
transmittance is determined each 10 nm in the range of 400-700 nm).
Spectra record The complete spectrum is recorded, and the entire spectrum, or a
part of it, is used for comparison. A modified method has been
suggested in which areas beneath an extinction curve represent
the colour intensity, being expressed as space units.
Table 11. Spectrophotometric methods for colour determination in dye solution or
dispersion, water and wastewater (adapted from Dos Santos et al., 2004).
In alkaline conditions (i.e. pH 9-12), at high temperatures (30-70ºC), and salt concentration
from 40-100 g/L, reactive dyes form a reactive vinyl sulfone (─SO3─CH═CH2) group, which
creates a bond with the fibres. However, the vinyl sulfone group undergoes hydrolysis (i.e. a
spontaneous reaction that occurs in the presence of water), and because the products do not
have any affinity with the fibres, they do not form a covalent bond (Dos Santos et al., 2004).
Therefore, a high amount of dye constituents are discharged in the wastewater.
The fixation efficiency varies with the class of azo dye used, which is around 98% for basic
dyes and 50% for reactive dyes (Table 12) (Bertea A. & Bertea A.P., 2008; O'Neill et al., 1999).
Large amounts of salts such as sodium nitrate, sodium sulphate and sodium chloride are
used in the dyebath, as well as sodium hydroxide that is widely applied to increase the pH
to the alkaline range. It is estimated that during the mercerising process the weight of these
salts can make up 20% of the fibre weight (EPA, 1997).
adequate treatment, the treated wastewater (WW) can either be discharged into a receiving
water body, into a subsequent central biological wastewater treatment plant (BWWTP) or a
municipal wastewater treatment plant (MWWTP).
Some selected treatment processes for dyes and colour removal of industrial wastewater
applied over the time into different textile units are summarized in Table 15. Some of these
methods will be further detail and some of authors’ results summarized.
Silica gels Pre treatment Effective for basic dyes Side reactions prevent
commercial application
Irradiation Post treatment Effective oxidation at lab scale Requires a lot of
dissolved oxygen (O2)
Photochemical Post treatment No sludge production Formation of by-
process products
Electrochemical Pre treatment No additional chemicals Cost intensive process;
oxidation required and the end products mainly high cost of
are non-dangerous/hazardous. electricity
Ion exchange Main Regeneration with low loss of Specific application; not
treatment adsorbents effective for all dyes
Biological treatments
Aerobic process Post treatment Partial or complete Expensive treatment
decolourization for all classes
of dyes
Anaerobic Main Resistant to wide variety of Longer acclimatization
process treatment complex coloured compounds. phase
Bio gas produced is used for
stream generation.
Single cell Post treatment Good removal efficiency for Culture maintenance is
(Fungal, Algal & low volumes and cost intensive. Cannot
Bacterial) concentrations. Very effective cope up with large
for specific colour removal. volumes of WW.
Emerging treatments
Other advanced Main Complete mineralization Cost intensive process
oxidation process treatment ensured. Growing number of
commercial applications.
Effective pre-treatment
methodology in integrated
systems and enhances
biodegradability.
Membrane Main Removes all dye types; High running cost.
filtration treatment recovery and reuse of chemicals Concentrated sludge
and water. production. Dissolved
solids are not separated
in this process
Photocatalysis Post treatment Process carried out at ambient Effective for small
conditions. Inputs are no toxic amount of coloured
and inexpensive. Complete compounds. Expensive
mineralization with shorter process.
detention times.
Sonication Pre treatment Simplicity in use. Very effective Relatively new method
in integrated systems. and awaiting full scale
application.
Enzymatic Post treatment Effective for specifically Enzyme isolation and
treatment selected compounds. purification is tedious.
Organic Pollutants Ten Years After
72 the Stockholm Convention – Environmental and Analytical Update
4.1.2 Irradiation
The irradiation treatment is a simple and efficient procedure for eliminating a wide variety
of organic contaminants, and as well disinfecting harmful microorganism using gamma rays
or electron beams (e.g., source for irradiation can be a monochromatic UV lamps working
under 253.7 nm). A high quantity of dissolved oxygen is required for an organic dye to be
effectively broken down by irradiation. The dissolved oxygen is consumed very rapidly and
so a constant and adequate supply is required. Irradiation treatment of a secondary effluent
from sewage treatment plant reduced COD, TOC and colour up to 64%, 34% and 88%
respectively, at a dose of 15 K Gy gamma-rays (Borrely et al., 1998). The efficiency of
irradiation treatment increases when is used catalyst as titanium dioxide (Krapfenbauer et
al., 1999). A lot of data are reported with the practical results obtained at the simple
exposure of different dye solutions or dispersions and dye-containing textile wastewaters to
sunlight for a period of a half, one or two months (direct photolysis with natural sunlight
into open basins). All these reports indicated high removals of colour (>84%), dye
destruction by photooxidation following first order kinetics at treatment of some vat dye
effluents. But the direct photolysis of textile organic dye in the natural aquatic environment
has proven difficult due to strong dependence of the decay rates on dye reactivity and
photosensitivity. Most of all commercial dyes are usually designed to be light resistant.
Therefore, the recent researches have been directed towards investigation of organic dye
photodegradation by sensitizers or catalysts in aqueous/dispersion systems by UV
irradiation. Moreover, there are reported high removal of indigo-colour when is initiated a
laser fading process for indigo coloured denim textile mainly based on basic interaction of
laser beam with indigo-coloured textile (Dascalu et al., 2000).
Micro-filtration is mainly used for treatment of dye baths containing pigment dyes as well
as for subsequent rinsing baths (Ramesh Babu et al., 2007). Chemicals that can not be
filtrated by microfiltration will remain in the dye bath. Microfiltration can be used as a
pretreatment for nanofiltration or reverse osmosis (Ghayeni et al., 1998), and also to separate
suspended solids, colloids from effluents or macromolecules with pores of 0.1 to 1 micron.
MF performance is typically of >90% for turbidity or silt density index. Microfiltration
membranes are made of specific polymers such as Poly (Ether Sulfone), Poly (Vinylidiene
Fluoride), Poly (Sulfone), Poly (Vinylidene Difluoride), Polycarbonate, Polypropylene, Poly
Tetrafluoroethylene (PTFE), etc. Ceramic, glass, carbon, zirconia coated carbon, alumina and
sintered metal membranes have been employed where extraordinary chemical resistance or
where high temperature operation is necessary. MF and UF operate at 20 to 100 psi
transmembrane pressures (Ptm) (low pressure membrane procees) and velocities of 20 to
100 cm/s (Naveed et al., 2006).
Ultra-filtration is used to separate macromolecules and particles, but the elimination of
polluting substances such as dyes is never complete (only 31-76% dye removal). The quality
of treated wastewater does not permit its reuse for sensitive processes, such as textile dyeing
(Ramesh Babu et al., 2007) but permit recycling of 40% treated wastewater in stages in which
salinity is not a problem, such as rinsing, washing, etc. Ultrafiltration can only be used as a
pretreatment for reverse osmosis (Ciardelli & Ranieri, 2001) or in combination with a
biological reactor (Mignani et al., 1999) or to remove metal hydroxides (reducing the heavy
metal content to 1 ppm or less) (Naveed et al., 2006). UF membranes are made of polymeric
materials (i.e. polysulfone, polypropylene, nylon-6, polytetrafluoroethylene (PTFE),
polyvinyl chlorides (PVC), acrylic copolymer etc.
Nano-Filtration was used for the treatment of coloured effluents from the textile industry,
mainly in a combination of adsorption (for decreasing of concentration polarization during
the filtration process) and nanofiltration (NF modules are extremely sensitive to fouling by
colloidal material and macromolecules). NF membranes are generally made of cellulose
acetate and aromatic polyamides, and retain low-molecular weight organic compounds,
divalent ions, large monovalent ions, hydrolized reactive dyes, and dyeing auxiliaries.
Inorganic materials, such as ceramics, carbon based membranes, zirconia, are also used in
manufacturing NF and RO membranes. Typical NF flux rates are 5 to 30 GFD (Gross Flow
per Day) (Naveed et al., 2006). A performance of above 70% colour removal for a NF plant
was reported working at 8 bar/18°C, with four polyethersulphonate membranes with
molecular weight cut offs of 40, 10, 5 and 3 kda for three different effluents coming from
dyeing cycle of textile industry (Alves & Pinho, 2000). Values of colour removal higher than
90% were reported for single NF process, and also combination MF and NF, in the case of
different effluents from textile fabrics processing. Harmful effects of high concentrations of
dye and salts in the dye house effluents were frequently reported (i.e. concentration of dye >
1.5 g/L, and of mineral salts >20 g/L) (Tang & Chen, 2002). An important problem is the
acculumation of dissolved solids, which makes discharge of treated effluents in
watercourses almost impossible. NF treatment can be an alternative fairly satisfactory for
textile effluent decolourization.
Reverse Osmosis is used to remove in a single step most types of ionic compounds,
hydrolized reactive dyes, chemical auxiliaries, and produce a high quality of permeate
(Ramesh Babu et al., 2007). Like NF, RO is very sensitive to fouling and the influent must be
carefully pretreated. RO membranes are generally made of cellulose acetate and aromatic
polyamides but also of inorganic materials. The Ptm in RO is typically 500 to 1000 psi, with
Organic Pollutants Ten Years After
76 the Stockholm Convention – Environmental and Analytical Update
cross flows of 20 to 100 cm/s. The range of typical RO fluxes is 5 to 15 GFD (Naveed et al.,
2006). In combination with physio-chemical treatment, the membrane processes has
advantages over the other conventional treatments, such as the ability to recover materials
with valuable recyclable water, reducting fresh water consumption and wastewater
treatment costs, small disposal volumes which minimizes waste disposal costs, reduction of
regulatory pressure and fine improved heat recovery systems. Membrane processes have
many cost-effective applications in textile industry.
Ozonation process. Ozone is a powerful oxidising agent (oxidation potential, E°= 2.07 V)
capable of cleavage the aromatic rings of some textile dyes and descomposition of other
organic pollutants from industrial effluents. The ozone decomposes the organic dyes with
conjugated double bonds forming smaller molecules with increased carcinogenic or toxic
properties, and so ozonation may be used alongside a physical method to prevent this (i.e.
irradiation, membrane separation, adsorption, etc). Ozone can react directly or indirectly
with dye molecules. In the direct pathway, the ozone molecule is itself the electron acceptor,
and hydroxide ions (i.e. pH > 7-8) catalyze the auto decomposition of ozone to hydroxyl
radicals (·OH) in aqueous effluents (very strong and non-selective oxidants) which react
with organic and inorganic chemicals. At low pH ozone efficiently reacts with unsaturated
chromophoric bonds of a dye molecule via direct reactions (Adams & Gorg, 2002).
The main advantage is that ozone can be applied in its gaseous state and therefore does not
increase the volume of wastewater and sludge. A disadvantage of ozonation is its short half-
life, tipically being 20 min, the destabilisation by the presence of salts, pH, and temperature,
and the additional costs for the installation of ozonation plant. The improvement of
ozonation preformance is obtained in combination with irradiation (Surpateanu & Zaharia,
2004a; Zaharia et al., 2009) or with a membrane filtration technique (Lopez et al., 1999).
Treatment of dye-containing wastewater with ozone followed by chemical coagulation
using Ca(OH)2 indicated 62% colour removal after ozonation (Sarasa et al., 1998).
Oxidation process with sodium hypochlorite. This treatment implies the attack at the
amino group of the dye molecule by Cl+, initiating and accelerating azo-bond cleavage. The
increasing of chlorine concentration favors the dye removal and decolourization process,
and also the decreasing of pH. The dye containing amino or substituted amino groups on
the naphthalene ring (i.e. dyes derived from amino-naphtol- and naphtylamino-sulphonic
acids) are most susceptible for chlorine decolourization (Omura, 1994). This treatment is
unsuitable for disperse dyes, and is becoming less frequent due to the negative effects at
releasing into watercourses of aromatic amines or otherwise toxic molecules. Moreover,
althought about 40% of the pigments used worldwise contain chlorine this corresponds to
only less than 0.02% of the total chlorine production (Slokar & Le Marechal, 1997).
Photochemical oxidation process. The UV treatment in the presence of H2O2 can
descomposed dye molecules to low weight organic molecules, or even to CO2, H2O, other
inorganic oxides, hydrides, etc. There can be also produced additional by-products such as
halides, metals, inorganic acids, organic aldehydes and organic acids depending on initial
materials and the extent of decolourisation treatment (Yang et al., 1998). The dye
decomposition is initiated by the generated hydroxyl radicals (H2O2 + hυ → 2HO·) and
hydroperoxide radicals (H2O2 + HO· → HO2· + H2O).
The treatment may be set-up in a batch or continuous column unit, and is influenced by the
intensity of the UV radiation, pH, dye structure and the dye bath composition (Slokar & Le
Marechal, 1997). The performance of photooxidation treatment in the presence of hydrogen
peroxide are high (i.e. >60-90% for colour removal, working with 400-500 mg/L H2O2 at pH
3-7, for Red M5B, H-acid and Blue MR dye-containing effluents) (Anjaneyulu et al., 2005) or
81-94% dye removal after 60 min, working with 88 mM H2O2 at pH of 4-6, for Acid Red G
dye-containing effluent (Surpateanu & Zaharia, 2004b; Zaharia et al., 2009).
Electrochemical oxidation process. As an advanced process, the electrochemical treatment
of dye-containing effluents is a potentially powerful method of pollution control, offering
high removal efficiencies (Anjaneyulu et al., 2005) especially for acid dyes as well as
Organic Pollutants Ten Years After
78 the Stockholm Convention – Environmental and Analytical Update
disperse and metal complex dyes. The main advantages of this treatment are considered the
requirement of simple equipment and operation, low temperature in comparison with other
non-electrochemical treatments, no requirement of any additional chemicals, easy control
but crucial for pH, the electrochemical reactors (with electrolytic cells) are compact, and
prevent the production of unwated by-products. The principal oxidising agent in
electrochemical process is hypochlorite ion or hypochlorous acid produced from naturally
occuring chloride ions. Hydroxyl radical and other reactive species also participate in
electrochemical oxidation of organics (Kim et al., 2002) that can be achieved directly or
indirectly at the anode. The breakdown compounds are generally not hazardous being
discharged into watercourses without important environmental and health risks.
The electrochemical oxidation is considered an efficient and economic treatment of recycling
textile wastewater for the dyeing stage. The environmental advantage mainly achieved is
the minimization of all emissions: emission of gases, solid waste, and liquid effluent. Other
important advantage is its capacity of adaptation to different volumes and pollution loads.
The main disadvantage is the generation of metallic hydroxide sludge (from the metallic
electrodes in the cell), that limits its use (Ramesh Babu et al., 2007).
Some studies reported colour removals of about 100% for dyeing wastewater within only 6
min of electrolysis (Vlyssides et al., 2000) (e.g., complete decolourization of textile effluent
containing blue-26 anthraquinone dye by electrochemical oxidation with lead dioxide
coated anode - Titanium Substract Insoluble Anode (TSIA), at neutral pH, in the presence of
sodium chloride, current density of 4.5 A/dm2, electrolysis time of 220 min, or maximum
95.2% colour and 72.5% COD removal of textile azo dye-containing effluent in a flow reactor
working at rate of 5 mL/min and current density of 29.9 mA/cm2) (Anjaneyulu et al., 2005).
4.2.3 Electrocoagulation
An advanced electrochemical treatment for dye and colour removal is electrocoagulation
(EC) that has as main goal to form flocs of metal hydroxides within the effluent to be
cleaned by electro-dissolution of soluble anodes. EC involves important processes as
electrolytic reactions at electrodes, formation of coagulants in aqueous effluent and
adsorption of soluble or colloidal pollutants on coagulants, and removal by sedimentation
and flotation. This treatment is efficient even at high pH for colour and COD removals being
strongly influenced by the current density and duration of reaction. The EC treatment was
applied with high efficiency for textile Orange II and Acid red 14 dye-containing effluents
(i.e. > 98% colour removal) (Daneshvar et al., 2003) or Yellow 86 dye-containing wastewater
(i.e. turbidity, COD, extractible substances, and dye removal of 87.20%, 49.89%, 94.67%, and
74.20%, after 30 min of operation, current intensity of 1 A, with monopolar electrodes)
(Zaharia et al, 2005) when iron is used as sacrificial anode. In general, decolorization
performance in EC treatment is between 90-95%, and COD removal between 30-36% under
optimal conditions (Ramesh Babu et al., 2007).
Organic Pollutants Ten Years After
80 the Stockholm Convention – Environmental and Analytical Update
subsequential anaerobic and aerobic bioreactor was able to completely remove the
sulphonated azo dye (i.e. MY10) at a maximum loading rate of 210 mg/L per day (Tan et
al., 2000). The degradation of azo dyes (i.e. Acid Red 151; Basic Blue 41; Basic Red 46, 16;
Basic Yellow 28, 19) in an aerobic biofilm system indicated 80% colour removal
(Anjaneyulu et al., 2005). The improvement of dye biodegradation performance (i.e. >90%
colour removal) are made by adding activated carbon (PAC) or bentonite in aeration tank.
5. Conclusions
The dyes are natural and synthetic compounds that make the world more beautiful through
coloured products but are also considered as pollutants of some water resources.
The textile sector will continue to be vitally important in the area of water conservation due
to its high consumption of water resources, and its individual or combined effluents’
treatments for no environmental pollution generation (i.e. polluting colourants).
The satisfaction of both discharge criteria for sewerage systems, watercourses and textile
reuse standards within economically viable limits implies critical analyses of industrial
effluents (total wastewater and raw reusable stream characterisation) and removal of all
pollutants from final effluents. The special category of organic pollutants - textile organic
dyes - must respect the strict limits in final effluents discharged or not in natural water
resources. This fact imposes the colour and/or dye removal from final effluents (especially
industrial effluents).
Dye removal from textile effluents in controlled conditions and strict reproductibility is an
environmental issue achievable by application of adequate mechano-physico-chemical and
also biological treatment procedures.
Textile Organic Dyes – Characteristics, Polluting Effects
and Separation/Elimination Procedures from Industrial Effluents – A Critical Overview 83
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